The present invention relates to novel, herbicidally active pyridine ketones, to their preparation, to compositions comprising these compounds, and to their use for controlling weeds, especially in crops of useful plants, or for inhibiting plant growth.
Herbicidally active pyridine ketones are described, for example, in WO 97/46530. There have now been found novel pyridine ketones which have herbicidal and growth-inhibitory properties.
The present invention therefore relates to compounds of the formula I 
in which
p is 0 or 1;
R5 is C1-C6haloalkyl; R2 is hydrogen, C1-C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, vinyl which is substituted by C1-C2alkoxycarbonyl or phenyl, or is C2-C6alkynyl, C2-C6haloalkynyl, ethynyl which is substituted by trimethylsilyl, hydroxyl, C1-C2alkoxy, C1-C2alkoxycarbonyl or phenyl, or is C3-C6allenyl, C3-C6cycloalkyl, C3-C6cycloalkyl which is substituted by halogen, or is C1-C6alkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, C1-C6haloalkoxy, C3-C6haloalkenyloxy, cyano-C1-C4alkoxy, C1-C4alkoxy-C1-C4alkoxy, C1-C4alkylthio-C1-C4alkoxy, C1-C4alkylsulfinyl-C1-C4alkoxy, C1-C4alkylsulfonyl-C1-C4alkoxy, C1-C4alkoxycarbonyl-C1-C4alkoxy, C1-6alkylthio, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylthio, C1-C6haloalkylsulfinyl, C1-C6haloalkylsulfonyl, C1-C4alkoxycarbonyl-C1-C4alkylthio, C1-C4alkoxycarbonyl-C1-C4alkylsulfinyl, C1-C4alkoxycarbonyl-C1-C4alkylsulfonyl, benzyl-S(O)n1xe2x80x94, C1-C6alkylamino, C2-C6dialkylamino, C1-C6alkylaminosulfonyl, di-(C1-C6alkylamino)sulfonyl, benzyloxy, benzyl, phenyl, phenoxy, phenylthio, phenylsulfinyl or phenylsulfonyl, it being possible for the phenyl-containing groups, in turn, to be substituted by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro or R2 is OS(O)n2xe2x80x94R21, N(R23)xe2x80x94S(O)n3xe2x80x94R22, cyano, carbamoyl, C1-C4alkoxycarbonyl, formyl, halogen, thiocyanato, amino, hydroxy-C1-C4alkyl, C1-C4alkoxy-C1-C4alkyl, C1-C4alkyl-S(O)n4xe2x80x94C1-C4alkyl, cyano-C1-C4alkyl, C1-C6alkylcarbonyloxy-C1-C4alkyl, C1-C4alkoxycarbonyl-C1-C4alkyl, C1-C4alkoxycarbonyloxy-C1-C4alkyl, C1-C4thiocyanato-C1-C4alkyl, benzoyloxy-C1-C4alkyl, C2-C6oxiranyl, C1-C4alkylamino, C1-C4alkyl, di-(C1-C4alkyl)amino-C1-C4alkyl, C1-C12alkylthiocarbonyl-C1-C4alkyl or formyl-C1-C4alkyl, or R2 is a five- to ten-membered monocyclic or fused bicyclic ring system which can be aromatic or partially saturated and can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, the ring system being bonded to the pyridine ring via a C1-C4alkylene, xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94Cxe2x89xa1Cxe2x80x94, xe2x80x94CH2Oxe2x80x94, xe2x80x94CH2N(C1-C4alkyl)xe2x80x94, xe2x80x94CH2SOxe2x80x94, or xe2x80x94CH2SO2 group and it not being possible for each ring system to contain more than 2 oxygen atoms and not more than 2 sulfur atoms, and it being possible for the ring system itself to be mono-, di- or trisubstituted by C1-C6alkyl, C1-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C1-C6alkoxy, C1-C6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, mercapto, C1-C6alkylthio, C1-C6haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, C2-C5alkoxyalkylthio, C3-C5acetylalkylthio, C3-C6alkoxycarbonylalkylthio, C2-C4cyanoalkylthio, C1-C6alkylsulfinyl, C1-C6haloalkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylsulfonyl, aminosulfonyl, C1-C2alkylaminosulfonyl, di-(C1-C2alkyl)aminosulfonyl, di-(C1-C4alkyl)amino, halogen, cyano, nitro, phenyl and benzylthio, it being possible for phenyl and benzylthio, in turn, to be substituted on the phenyl ring by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro, and substituents on the nitrogen in the heterocyclic ring being other than halogen;
R3 is hydrogen, C1-C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C-C6alkynyl, C2-C6haloalkynyl, C3-C6cycloalkyl, C1-C6alkoxy, C1-C6haloalkoxy, C1-C6alkylthio, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylthio, C1-C6haloalkylsulfinyl, C1-C6haloalkylsulfonyl, C1-C6alkylamino, C2-C6dialkylamino, C1-C6alkylaminosulfonyl, C2-C6dialkylaminosulfonyl, phenyl, phenylthio, phenylsulfinyl, phenylsulfonyl or phenoxy, it being possible for phenyl, in turn, to be substituted by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro, or R3 is xe2x80x94N(R23)xe2x80x94S(O)nxe2x80x94R22, cyano, halogen, amino, C1-C4alkoxy-C1-C4alkyl or C1-C4alkyl-S(O)nxe2x80x94C1-C4alkyl;
R4 is hydrogen, C1-C6alkyl, hydroxyl, C1-C6alkoxy, C1-C6haloalkoxy, C3-C6alkenyloxy, C3-C6haloalkenyloxy, C3-C6alkynyloxy, C1-C4alkylcarbonyloxy, C1-C4alkylsulfonyloxy, tosyloxy, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, C1-C4alkylamino, C1-C4dialkylamino, C1-C4alkoxycarbonyl, C1-C4haloalkyl, formyl, cyano, halogen, phenyl or phenoxy, it being possible for phenyl, in turn, to be substituted by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro;
or R4 is a five to ten-membered monocyclic or R3-fused bicyclic ring system which can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, the ring system, unless fused, being bonded to the pyridine ring directly or via a C1-C4alkylene, xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94Cxe2x89xa1Cxe2x80x94, xe2x80x94CH2Oxe2x80x94, xe2x80x94CH2N(C1-C4alkyl)xe2x80x94, xe2x80x94CH2Sxe2x80x94, xe2x80x94CH2SOxe2x80x94, or xe2x80x94CH2SO2xe2x80x94 group and it not being possible for the ring system to contain more than 2 oxygen atoms and not more than two sulfur atoms, and it being possible for the ring system itself to be mono-, di- or trisubstituted by C1-C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C1-C6alkoxy, C1-C6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, C1-C6alkylthio, C1-C6haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenyl C3-C6alkynylthio, C1-C4alkoxy-C1-C2alkylthio, C1-C4alkylcarbonyl-C1-C2alkylthio, C1-C4alkoxycarbonyl-C1-C2alkylthio, cyano-C1-C4alkylthio, C1-C6alkylsulfinyl, C1-C6haloalkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylsulfonyl, aminosulfonyl, C1-C2alkylaminosulfonyl, di-(C1-C2alkyl)aminosulfonyl, di-(C1-C4alkyl)amino, halogen, cyano, nitro, phenyl and benzylthio, it being possible for phenyl and benzylthio, in turn, to be substituted on the phenyl ring by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro, and substituents on the nitrogen in the heterocyclic ring being other than halogen;
R21 is C1-C4alkyl or C1-C4haloalkyl;
R22 is C1-C4alkyl, C1-C4haloalkyl or di-(C1-C4alkyl)amino;
R23 R24, R25 independently of one another are hydrogen or C1-C4alkyl;
n, n1, n2, n3 and n4 independently of one another are 0, 1 or 2;
Q is Q1
xe2x80x83in which
R6, R7, R8 and R9 independently of one another are hydrogen, C1-C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, C2-C6alkynyl, C1-C6alkoxycarbonyl, C1-C6alkylcarbonyl, C1-C6alkyl-S(O)n17, C1-C6alkyl-NHS(O)2, C1-C6alkylamino, di-(C1-C6alkyl)amino, hydroxyl, C1-C6alkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, hydroxy-C1-C6alkyl, C1-C4alkylsulfonyloxy-C1-C6alkyl, tosyloxy-C1-C6alkyl, C1-C6alkoxy-C1-C6alkyl, C1-C6alkyl-S(O)n4-C1-C6alkyl, cyano-C1-C6alkyl, C1-C6alkoxy-C1-C6alkoxy, benzyloxy-C1-C6alkyl, C1-C6alkoxycarbonyl-C1-C6alkyl, C1-C6alkoxycarbonyloxy-C1-C6alkyl, thiocyanato-C1-C6alkyl, oxiranyl, C1-C6alkylamino-C1-C6alkyl, di(C1-C6alkyl)amino-C1-C6alkyl, formyl-C1-C6alkyl, C1-C6alkyloximo, halogen, cyano, nitro, phenyl or phenyl which is substituted by C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, amino, C1-C4alkylamino, di-C1-C4alkylamino, C1-C4alkyl-S(O)n18, C1-C4alkyl-S(O)2O, C1-C4haloalkyl-S(O)n5, C1-C4haloalkyl-S(O)2O, C1-C4alkyl-S(O)2NH, C1-C4alkyl-S(O)n19N(C1-C4alkyl2, halogen, nitro, COOH or cyano;
or adjacent R6 and R7 or R8 and R9 together are xe2x80x94(CH2)mxe2x80x94, C(O)O(CH2)n20xe2x80x94 or xe2x80x94S(O)n21(CH2)n22xe2x80x94;
n5, n17, n18, n19 and n21 independently of one another are 0, 1 or 2;
n20 is 2 or 3;
n22 is 2, 3 or 4;
m is 2, 3, 4, 5, or 6;
W is oxygen, S(O)n6, xe2x80x94CR11R12, xe2x80x94CR63R64CR65R66, xe2x80x94C(O)xe2x80x94 or xe2x80x94NR13;
R63, R64, R65 and R66 independently of one another are hydrogen or C1-C6alkyl, or R65 together with R7 or R9 forms a direct bond;
n6 is 0, 1 or 2;
R11 is hydrogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy-C1-C4alkyl, C1-C4alkylthio-C1-C4alkyl, C1-C4alkylthio-C3-C6cycloalkyl, C1-C4alkycarbonyloxy-C1-C4alkyl, C1-C4alkysulfonyloxy-C1-C4alkyl, tosyloxy-C1-C4alkyl, di-(C1-C3alkoxyalkyl)methyl, di-(C1-C3alkthioalkyl)methyl, (C1-C3alkoxyalkyl)-(C1-C3alkthioalkyl)methyl, C3-C5oxacycloalkyl, C3-C5thiacycloalkyl, C3-C4dioxacycloalkyl, C3-C4dithiacycloalkyl, C3-C4oxathiacycloalkyl, formyl, C1-C4alkoxycarbonyl, carbamoyl, C1-C4alkylaminocarbonyl, di-(C1-C4alkyl)aminocarbonyl, phenylaminocarbonyl, benzylaminocarbonyl or phenyl which, in turn, can be substituted by C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, amino, C1-C4alkylamino, di-C1-C4alkylamino, C1-C4alkyl-S(O)n21, C1-C4alkyl-S(O)2O, C1-C4haloalkyl-S(O)n7, C1-C4haloalkyl-S(O)2O, C1-C4alkyl-S(O)2NH, C1-C4alkyl-S(O)n20N(C1-C4alkyl), halogen, nitro, COOH or cyano;
n7, n20 and n21 independently of one another are 0, 1 or 2;
or R12 together with R6 or R9 is a group xe2x80x94(CH2)oxe2x80x94;
o is 1, 2, 3, 4 or 5;
R12 is hydrogen, C1-C4alkyl or C1-C4haloalkyl;
or R12 together with R1i is a group xe2x80x94(CH2)m1;
m, is 2, 3, 4, 5, or 6;
R10 is hydroxyl, Oxe2x88x92M+, halogen, cyano, SCN, OCN, C1-C12alkoxy, C1-C4alkoxycarbonyl-C1-C4alkoxy, C1-C12alkylthio, C1-C12alkylsulfinyl, C1-C12alkylsulfonyl, C1-C12haloalkylthio, C1-C12haloalkylsulfinyl, C1-C12haloalkylsulfonyl, C1-C6alkoxy-C1-C6alkylthio, C1-C6alkoxy-C1-C6alkylsulfinyl, C1-C6alkoxy-C1-C6alkylsulfonyl, C2-C12alkenylthio, C2-C12alkenylsulfinyl, C2-C12alkenylsulfonyl, C2-C12alkynylthio, C2-C12alkynylsulfinyl, C2-C12alkynylsulfonyl, C2-C12haloalkenylthio, C2-C12haloalkenylsulfinyl, C2-C12haloalkenylsulfonyl, C1-C4alkoxycarbonyl-C1-C4alkylthio, C1-C4alkoxycarbonyl-C1-C4alkylsulfinyl, C1-C4alkoxycarbonyl-C1-C4alkylsulfonyl, (C1-C4alkoxy)2P(O)O, C1-C4alkyl-(C1-C4alkoxy)P(O)O, H(C1-C4alkoxy)P(O)O, R14R15N, R14R15NNH, R16R17NC(O)Oxe2x80x94, R16R17NC(O)NHxe2x80x94, C1-C12alkyl-S(O)2NR18, C1-C4haloalkyl-S(O)2NR19, C1-C12alkyl-S(O)2O, C1-C4haloalkyl-S(O)2O, C1-C18alkylcarbonyloxy, it being possible for the alkyl group to be substituted by halogen, C1-C6alkoxy, C1-C6alkylthio or cyano, or is C2-C18alkenylcarbonyloxy, C2-C18alkynylcarbonyloxy, C3-C6cycloalkylcarbonyloxy, C1-C12alkoxycarbonyloxy, C1-C12alkylthiocarbonyloxy, C1-C12alkylthiocarbamoyl, C1-C6alkyl-NH(CS)N(C1-C6alkyl)xe2x80x94NHxe2x80x94, di-C1-C6alkyl-N(CS)N(C1-C6alkyl)xe2x80x94NHxe2x80x94, benzyloxy, benzylthio, benzylsulfinyl, benzylsulfonyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenylsulfonylamino, phenylsulfonyloxy or benzoyloxy, it being possible for the phenyl groups, in turn, to be substituted by C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, C1-C4alkylamino, di-C1-C4alkylamino, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, C1-C4alkyl-S(O)2O, C1-C4haloalkylthio, C1-C4haloalkylsulfinyl, C1-C4haloalkylsulfonyl, C1-C4haloalkyl-S(O)2O, C1-C4alkyl-S(O)2NH, C1-C4alkyl-S(O)2N(C1-C4alkyl), halogen, nitro or cyano;
or R10 is a group Ar1-thio, Ar2-sulfinyl, Ar3-sulfonyl, xe2x80x94OCOxe2x80x94Ar4 or NHxe2x80x94Ar5 in which Ar1, Ar2, Ar3, Ar4 and Ar5 independently of one another are a five- to ten-mnembered monocyclic or fused bicyclic ring system which can be aromatic or partially saturated and can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, and it being possible for each ring system to contain not more than 2 oxygen atoms and not more than two sulfur atoms, and it being possible for the ring system itself to be mono-, di- or trisubstituted by C1-C6alkyl, C1-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C1-C6alkoxy, C1-C6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, mercapto, C1-C6alkylthio, C1-C6haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, C2-C5alkoxyalkylthio, C3-C5acetylalkylthio, C3-C6alkoxycarbonylalkylthio, C2-C4cyanoalkylthio, C1-C6alkylsulfinyl, C1-C6haloalkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylsulfonyl, aminosulfonyl, C1-C2alkylaminosulfonyl, di-(C1-C2alkyl)aminosulfonyl, di-(C1-C4alkyl)amino, halogen, cyano, nitro, phenyl and benzylthio, it being possible for phenyl and benzylthio, in turn, to be substituted on the phenyl ring by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro, and where substituents on the nitrogen in the heterocyclic ring are other than halogen;
R14, R15, R16, R17 and R18 independently of one another are hydrogen or C1-C6alkyl;
n8, n9, n10, n11, n12, n13 and n14 independently of one another are 0, 1 or 2;
R13 is hydrogen, C1-C4alkyl, C1-C4alkythio-C1-C4carbonyl, C1-C4alkylsulfinyl-C1-C4carbonyl, C1-C4alkylsulfonyl-C1-C4carbonyl, C1-C4alkoxycarbonyl, C1-C4alkylcarbonyl, phenylcarbonyl, or is phenyl which, in turn, can be substituted by C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, C1-C4alkylamino, di-C1-C4alkylamino, C1-C4alkyl-S(O)n15, C1-C4alkyl-S(O)2O, C1-C4haloalkyl-S(O)n16, C1-C4haloalkyl-S(O)2O, C1-C4alkyl-S(O)2NH, C1-C4alkyl-S(O)2N(C1-C4alkyl), halogen, nitro, or cyano; and
n15 and n16 independently of one another are 0, 1 or 2;
and the agrochemically tolerated salts M+ and all stereoisomers and tautomers of the compounds of the formula I.
The alkyl groups in the definitions of the substituents can be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl and their branched isomers. Alkoxy, alkenyl and alkynyl radicals are derived from the abovementioned alkyl radicals. The alkenyl and alkynyl groups can be mono- or polyunsaturated.
An alkylene group for example, xe2x80x94(CH2)mxe2x80x94, xe2x80x94(CH2)m1xe2x80x94 or xe2x80x94(CH2)oxe2x80x94 can be substituted by one or more methyl group; preferably, such alkylene groups are in each case unsubstituted. The same also applies to the xe2x80x94C(O)O(CH2)n20xe2x80x94 and xe2x80x94S(O)n21(CH2)n22xe2x80x94 group and to all C3-C6cycloalkyl-, C3-C5oxacycloalkyl-, C3-C5thiacycloalkyl-, C3-C4dioxacycloalkyl-, C3-C4dithiacycloalkyl-, C3-C4oxathiacycloalkyl-containing groups.
Halogen is, as a rule, fluorine, chlorine, bromine or iodine. This also applies analogously to halogen in conjunction with other meanings such as haloalkyl or halophenyl.
Haloalkyl groups with a chain length of 1 up to 6 carbon atoms are, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 1-fluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2-fluoroprop-2-yl, pentafluoroethyl, 1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl, pentafluoroethyl, heptafluoro-n-propyl, perfluoro-n-hexyl; haloalkyl groups in the meanings R2, R3 and, in particular, R5 are preferably trichloromethyl, fluoromethyl, dichlorofluoromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl, pentafluoroethyl or heptafluoro-n-propyl.
Suitable as haloalkyl are monohalogenated or polyhalogenated alkenyl groups, where halogen is fluorine, chlorine, bromine and iodine, and in particular fluorine and chlorine, for example 1-chlorovinyl, 2-chlorovinyl, 2,2-difluorovinyl, 2,2-difluoroprop-1-en-2-yl, 2,2-dichlorovinyl, 3-fluoroprop-1-enyl, chloroprop-1-en-1-yl, 3-bromoprop-1-en-1-yl, 2,3,3-trifluoroprop-2-en-1-yl, 2,3,3-trichloroprop-2-en-1-yl and 4,4,4-trifluorobut-2-en-1-yl. Preferred amongst the monohalogenated, dihalogenated or trihalogenated C2-C6alkenyl groups are those which have a chain length of 2 to 5 carbon atoms.
Suitable as haloalkynyl are, for example, monohalogenated or polyhalogenated alkynyl groups, where halogen is bromine, iodine and, in particular, fluorine and chlorine, for example 3-fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoropropynyl and 4,4,4-trifluorobut-2-yn-1-yl. Preferred amongst the monohalogenated or polyhalogenated alkynyl groups are those which have a chain length of 2 to 5 carbon atoms.
A monohalogenated or polyhalogenated C3-C6cycloalkyl group is, for example, the 2,2-dichlorocyclopropyl, 2,2-dibromocyclopropyl, 2,2,3,3-tetrafluorocyclobutyl or 2,2-difluoro-3,3-dichlorocyclobutyl group.
Alkoxy groups preferably have a chain length of 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, i-propoxy, n-butoxy, iso-butoxy, sec-butoxy and tert-butoxy and the pentyloxy and hexyloxy isomers; preferably methoxy and ethoxy. Alkylcarbonyl is preferably acetyl or propionyl. Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, iso-propoxycarbonyl, n-butoxycarbonyl, iso-butoxycarbonyl, sec-butoxycarbonyl or tert-butoxycarbonyl; preferably methoxycarbonyl, ethoxycarbonyl or tert-butoxycarbonyl. Haloalkoxy groups preferably have a chain length of 1 to 6 carbon atoms.
Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2-trichloroethoxy; preferably fluoromethoxy, difluoromethoxy, 2-chloroethoxy and trifluoromethoxy.
Alkylthio groups preferably have a chain length of 1 to 8 carbon atoms. Alkylthio is, for example, methylthio, ethylthio, propylthio, iso-propylthio, n-butylthio, iso-butylthio, sec-butylthio or tert-butylthio, preferably methylthio and ethylthio. Alkylsulfinyl is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, iso-propylsulfinyl, n-butylsulfinyl, iso-butylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl; preferably methylsulfinyl and ethylsulfinyl.
Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, iso-propylsulfonyl, n-butylsulfonyl, iso-butylsulfonyl, sec-butylsuIfonyl or tert-butylsulfonyl; preferably methylsulfonyl or ethylsulfonyl.
Alkylamino is, for example, methylamino, ethylamino, n-propylamino, iso-propylamino or the butylamino isomers. Dialkylamino is, for example, dimethylamino, methylethylamino, diethylamino, n-propylmethylamino, di-butylamino and di-iso-propylamino. Preferred are alkylamino groups having a chain length of 1 to 4 carbon atoms. Alkoxyalkyl groups preferably have 1 to 6 carbon atoms. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, iso-propoxymethyl or iso-propoxyethyl. Alkylthioalkyl groups preferably have 1 to 6 carbon atoms. Alkylthioalkyl is, for example, methylthiomethyl, methylthioethyl, ethylthiomethyl, ethylthioethyl, n-propylthiomethyl, n-propylthioethyl, iso-propylthiomethyl, iso-propylthioethyl, butylthiomethyl, butylthioethyl or butylthiobutyl.
Phenyl, also as part of a substituent such as phenoxy, benzyl, benzyloxy, benzoyl, phenylthio, phenylalkyl, phenoxyalkyl or tosyl can be in monosubstituted or polysubstituted form. In this case, the substituents can be in any of the ortho, meta and/or para position(s).
Allenyl is, for example, CH2xe2x95x90Cxe2x95x90CH2CH2xe2x95x90CHxe2x80x94CH2xe2x80x94CHxe2x95x90CH2, CH2xe2x95x90CHxe2x80x94CH2xe2x80x94CH2xe2x80x94CH2xe2x80x94CHxe2x95x90CH2 or CH2xe2x95x90CHxe2x80x94CH2xe2x80x94CHxe2x95x90CHxe2x80x94CH3.
The invention also extends to the salts M+which the compounds of the formula I, in particular those compounds of the formula I in which R10 is Oxe2x88x92M+, can form, preferably with amines, alkali metal bases, alkaline earth metal bases or quaternary ammonium bases. The following must be emphasized as salt formers amongst the alkali metal bases and alkaline earth metal bases: the hydroxides of lithium, sodium, potassium, magnesium or calcium, in particular those of sodium or potassium. Examples of amines which are suitable for ammonium salt formation are not only ammonia, but also primary, secondary and tertiary C1-C18alkylamines, C1-C4hydroxyalkylamines and C2-C4alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, iso-propylamine, the four butylamine isomers, n-amylamine, iso-amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonylamine, methyl-pentadecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine, diethylamine, di-n-propylamine, di-iso-propylamine, di-n-butylamine, di-n-amylamine, di-iso-amylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, iso-propanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, tri-iso-propylamine, tri-n-butylamine, tri-iso-butylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines for example, pyridine, quinoline, iso-quinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines for example anilines, methoxyanilines, ethoxyanilines, o-, m-, p-toluidines, phenylenediamines, naphthylamines and o-, m- and p-chloroanilines; but in particular triethylamine, iso-propylamine and di-iso-propylamine. Examples of quaternary ammonium bases which are suitable for salt formation are, for example, [N(RaRbRcRd)]+OHxe2x88x92, where Ra, Rb, Rc and Rd independently of one another are C1-C4alkyl. Other suitable tetraalkylammonium bases with other anions can be obtained, for example, by anion exchange reactions. M+ preferably represents an ammonium salt, in particular NH4+, or an alkali metal, in particular potassium or sodium.
The compounds of the formula I can occur in various tautomeric forms, for example, if R10 is hydroxyl, in the preferred formulation Ixe2x80x2 and Ixe2x80x2xe2x80x3
Preferred among the compounds of the formula I are those in which
p is 0;
R5 is C1-C6haloalkyl;
R2 is hydrogen, C1-C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C3-C6cycloalkyl, C1-C6alkoxy, C1-C6haloalkoxy, C1-C6alkylthio, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylthio, C1-C6haloalkylsulfinyl, C1-C6haloalkylsulfonyl, benzyl-S(O)n1xe2x80x94, C1-C6alkylamino, C2-C6dialkylamino, C1-C6alkylaminosulfonyl, C2-C6dialkylaminosulfonyl, phenyl, phenoxy, phenylthio, phenylsulfinyl or phenylsulfonyl, it being possible for the phenyl group, in turn, to be substituted by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro, or is OS(O)n2xe2x80x94R21, N(R23)xe2x80x94S(O)n3xe2x80x94R2, cyano, halogen, amino, C1-C4alkoxy-C1-C4alkyl, C1-C4alkyl-S(O)n4xe2x80x94C1-C4alkyl, cyano-C1-C4alkyl or C1-C4alkoxy-C1-C4alkoxy;
R3 is hydrogen, C1-C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C3-C6cycloalkyl, C1-C6alkoxy, C1-C6haloalkoxy, C1-C6alkylthio, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylthio, C1-C6haloalkylsulfinyl, C1-C6haloalkylsulfonyl, C1-C6alkylamino, C2-C6dialkylamino, C1-C6alkylaminosulfonyl, C2-C6dialkylaminosulfonyl, phenyl, phenylthio, phenylsulfinyl, phenylsulfonyl or phenoxy, it being possible for phenyl, in turn, to be substituted by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro, or is xe2x80x94N(R23)xe2x80x94S(O)nxe2x80x94R22, cyano, halogen, amino, C1-C4alkoxy-C1-C4alkyl or C1-C4alkyl-S(O)nxe2x80x94C1-C4alkyl;
R4 is hydrogen, C1-C6alkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylcarbonyloxy, C1-C4alkylthio, CG-C4alkylsulfinyl, C1-C4alkylsulfonyl, C1-C4haloalkyl, formyl, cyano, halogen, phenyl or phenoxy, it being possible for phenyl, in turn, to be substituted by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro;
or R4 is a five- to ten-membered monocyclic or R3-fused bicyclic ring system which can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, the ring system being bonded to the pyridine ring via a C1-C4alkylene group and it not being possible for the ring system to contain more than 2 oxygen atoms and not more than two sulfur atoms, and it being possible for the ring system itself to be mono-, di- or trisubstituted by C1-C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C1-C6alkoxy, C1-C6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, C1-C6Alkylthio, C1-C6haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, C1-C4alkoxy-C1-C2alkylthio, C1-C4alkylcarbonyl-C1-C2alkylthio, C1-C4alkoxycarbonyl-C1-C2alkylthio, cyano-C1-C4alkylthio, C1-C6alkylsulfinyl, C1-C6haloalkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylsulfonyl, aminosulfonyl, C1-C2alkylaminosulfonyl, C2-C4dialkylaminosulfonyl, halogen, cyano, nitro, phenyl and benzylthio, it being possible for phenyl and benzylthio, in turn, to be substituted on the phenyl ring by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro, and where substituents on the nitrogen in the heterocyclic ring are other than halogen;
R21 and R22 independently of one another are C1-C4alkyl or C1-C4haloalkyl;
R23, R24 and R25 independently of one another are hydrogen or C1-C4alkyl;
n, n1, n2, n3 and n4 independently of one another are 0, 1 or 2;
Q is 01
xe2x80x83in which
R6, R7, R8 and R9 independently of one another are hydrogen, C1-C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, C2-C6alkynyl, C1-C6alkoxycarbonyl, C1-C6alkyl-S(O)n17, C1-C6alkyl-NHS(O)2, C1-C6alkylamino, di-(C1-C6alkyl)amino, hydroxyl, C1-C6alkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, hydroxy-C1-C6alkyl, C1-C4alkylsulfonyloxy-C1-C6alkyl, tosyloxy-C1-C6alkyl, halogen, cyano, nitro, phenyl or phenyl which is substituted by C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, amino, C1-C4alkylamino, di-C1-C4alkylamino, C1-C4alkyl-S(O)n18, C1-C4alkyl-S(O)2O, C1-C4haloalkyl-S(O)n5, C1-C4haloalkyl-S(O)2O, C1-C4alkyl-S(O)2NH, C1-C4alkyl-S(O)n19N(C1-C4alkyl), halogen, nitro, COOH or cyano;
or adjacent R6 and R7 or R8 and R9 together are xe2x80x94(CH2)mxe2x80x94;
n5 n17, n18 and n19 independently of one another are 0, 1 or 2;
m is 2, 3, 4, 5, or 6;
W is oxygen, S(O)n6, xe2x80x94CR11, R12xe2x80x94, xe2x80x94C(O)xe2x80x94 or xe2x80x94NR13xe2x80x94;
n6 is 0, 1 or 2;
R11 is hydrogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy-C1-C4alkyl, C1-C4alkylthio-C1-C4alkyl, C1-C4alkylcarbonyloxy-C1-C4alkyl, C1-C4alkylsulfonyloxy-C1-C4alkyl, tosyloxy-C1-C4alkyl, di-(C1-C3alkoxyalkyl)methyl, di-(C1-C3alkylthioalkyl)methyl, (C1-C3alkoxyalkyl)-(C1-C3alkylthioalkyl)methyl, C3-C5oxacycloalkyl, C3-C5thiacycloalkyl, C3-C4dioxacycloalkyl, C3-C4dithiacycloalkyl, C3-C4oxathiacycloalkyl, formyl, C1-C4alkoxycarbonyl or phenyl which, in turn, can be substituted by C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, amino, C1-C4alkylamino, di-C1-C4alkylamino, C1-C4alkyl-S(O)n21, C1-C4alkyl-S(O)2O, C1-C4haloalkyl-S(O)n7, C1-C4haloalkyl-S(O)2O, C1-C4alkyl-S(O)2NH, C1-C4alkyl-S(O)n20N(C1-C4alkyl), halogen, nitro, COOH or cyano;
n7, n20 and n21 independently of one another are 0, 1 or 2;
or R12 together with R9 is a group xe2x80x94(CH2)oxe2x80x94;
o is 1, 2, 3, 4 or 5;
R12 is hydrogen, C1-C4alkyl or C1-C4haloalkyl;
or R12 together with R11 is a group xe2x80x94(CH2)m1;
m1 is 2, 3, 4, 5, or 6;
R10 is hydroxyl, Oxe2x88x92M+, halogen, C1-C12alkoxy, C1-C12alkylcarbonyloxy, C2-C4alkenylcarbonyloxy, C3-C6cycloalkylcarbonyloxy, C1-C12alkoxycarbonyloxy, C1-C12alkylcarbonyloxy, R23R24Nxe2x80x94C(O)O, C1-C12alkylS(O)n8xe2x80x94, C1-C4haloalkyl-S(O)n9xe2x80x94, C2-C12alkenylS(O)n10xe2x80x94, C2-C12haloalkenylS(O)n11xe2x80x94, C2-C12alkynylS(O)n12xe2x80x94; benzyloxy, phenoxy, phenylthio, phenylsulfinyl or phenylsulfonyl, where the phenyl group, in turn, can be substituted by C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, C1-C4alkylamino, di-C1-C4alkylamino, C1-C4alkyl-S(O)n13, C1-C4alkyl-S(O)2O, C1-C4haloalkyl-S(O)n14, C1-C4haloalkyl-S(O)2O, C1-C4alkyl-S(O)2NH, C1-C4alkyl-S(O)2N(C1-C4alkyl), halogen, nitro or cyano, or is C1-C4alkyl-S(O)2O, phenyl-S(O)2O, C1-C4alkoxy)2P(O)O, C1-C4alkyl(C1-C4alkoxy)P(O)O, or H(C1-C4alkoxy)P(O)O;
n8, n9, n10, n11, n12, n11 and n14 independently of one another are 0, 1 or 2;
R13 is hydrogen, C1-C4alkyl, C1-C4alkoxycarbonyl or phenyl which, in turn, can be substituted by C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, C1-C4alkylamino, di-C1-C4alkylamino, C1-C4alkyl-S(O)n15, C1-C4alkyl-S(O)2O, C1-C4haloalkyl-S(O)n16, C1-C4haloalkyl-S(O)2O, C1-C4alkyl-S(O)2NH, C1-C4alkyl-S(O)2N(C1-C4alkyl), halogen, nitro or cyano;
n15 and n16 independently of one another are 0, 1 or 2;
and the agrochemically tolerated salts M+and all stereoisomers and tautomers of the compounds of the formula I.
In a preferred group of compounds of the formula I, R10 is halogen, thiocyanato, C1-C12alkylthio, C1-C12alkylsulfinyl, C1-C12alkylsulfonyl, C1-C12haloalkylthio, C1-C12haloalkylsulfinyl, C1-C12haloalkylsulfonyl, C1-C12alkenylthio, C2-C12alkenylsulfinyl, C2-C12alkenylsulfonyl, C2-C12haloalkenylthio, C2-C12haloalkenylsulfinyl, C2-C12-haloalkenylsulfonyl, C2-C12alkynylthio, C2-C12alkynylsulfinyl, C2-C12alkynylsulfonyl, C1-C4alkoxycarbonyl-C1-C2alkylthio, C1-C4alkoxycarbonyl-C1-C2alkylsulfinyl, C1-C4alkoxycarbonyl-C1-C2alkylsulfonyl, C1-C8alkyl-S(O)2NH, C1-C8haloalkyl-S(O)2NH, C1-C8alkyl-S(O)2O, C1-Cl8alkylcarbonyloxy, C2-C18alkenylcarbonyloxy, C3-C6cycloalkylcarbonyloxy, C1-C12alkoxycarbonyloxy, C1-C12alkylthiocarbonyloxy, R16R17NC(O)Oxe2x80x94, R16R17NC(S)Oxe2x80x94, benzylthio, benzylsulfinyl, benzylsulfonyl, phenylthio, phenylsulfinyl, phenylsulfonyl, phenylsulfonyloxy or benzoyloxy, it being possible for the phenyl groups, in turn, to be substituted as indicated in claim 1; or is a group Ar1-thio, Ar1-sulfinyl, Ar1-sulfonyl in which Ar1 is a five- or six-membered monocyclic ring system which can be aromatic or partially saturated and can contain 1 to 2 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur and which, in turn, can be substituted as indicated in claim 1; or is thienylcarbonyloxy or furylcarbonyloxy, it being possible for these, in turn, to be substituted by methyl or halogen, or pyridylcarbonyloxy which, in turn, can be substituted as indicated in claim 1.
In preferred compounds of the formula I, furthermore, R10 is hydroxyl or Oxe2x88x92M+.
Other compounds of the formula I which must be emphasized are those in which W is oxygen, xe2x80x94CR11R12xe2x80x94 or xe2x80x94C(O)xe2x80x94, where, in particular when W is xe2x80x94CR11R12xe2x80x94,
a) R6 is hydrogen, methyl, ethyl, cyano, methoxycarbonyl, ethoxycarbonyl, methylthio, methylsulfinyl, methylsulfonyl or methoxy; and R7, R8, R9, R1, and R12 independently of one another are hydrogen, C1-C4alkyl, C1-C3haloalkyl, C2-C3alkenyl or C2-C3alkynyl, or
b) adjacent R6 and R7 and/or R8 and R9 together are xe2x80x94(CH2)mxe2x80x94, xe2x80x94C(O)O(CH2)2xe2x80x94 or S(O)n21(CH2)3xe2x80x94; or
c) R6 is hydrogen, methyl, ethyl, methoxycarbonyl, ethoxycarbohyl, methylthio, methylsulfinyl, methylsulfonyl or methoxy and R12 together with R9 is xe2x80x94(CH2)oxe2x80x94.
Furthermore, preferred groups of compounds of the formula I are those in which
W is oxygen and R6, R7, R8 and R9 independently of one another are hydrogen or C1-C3alkyl; or
W is xe2x80x94C(O)xe2x80x94 and R6, R7, R8 and R9 independently of one another are C1-C3alkyl; or
R2 is hydrogen and R3 is methyl; or
R2 is methyl, ethyl, n-propyl, i-propyl, vinyl, methoxymethyl, methoxycarbonyloxymethyl, ethoxycarbonyloxymethyl, acetoxymethyl, propionyloxymethyl, chloromethyl, bromomethyl, fluoromethyl, difluoromethyl, trifluoromethyl or cyanomethyl.
Other compounds of the formula I which must be emphasized are those in which R4 is hydrogen or methyl or R5 is trifluoromethyl, difluorochloromethyl, pentafluoroethyl, heptafluoropropyl or difluoromethyl.
In a further preferred group of compounds of the formula I, R3 is hydrogen, R2 is C1-C4alkyl, C1-C3haloalkyl, cyclopropyl, C2-C3alkenyl, C2-C3haloalkenyl, C2-C3alkynyl, allenyl, C1-C2-alkoxy-C1-C2alkyl, C1-C2alkylthio-C1-C2alkyl, cyano-C1-C2alkyl, C1-C2alkoxycarbonyl-C1-C2alkyl, C1-C4alkylcarbonyloxy-C1-C2alkyl, C1-C3alkoxy, C1-C3haloalkoxy, allyloxy, propargyloxy, C1-C3alkylthio, C1-C3alkylsulfinyl or cyano.
The compounds of the formula I in which Q is a group Q1 can be prepared using processes which are known per se, for example those described in EP-A-0 353 187 and EP-A-0 316 491, for example either by
a) reacting a compound of the formula III 
in which R2, R3, R4 and R5 have the meaning given under formula I and X is a leaving group, for example halogen or cyano, with a compound of the formula II 
in which R6, R7, R8, R9 and W have the meaning given under formula I in the presence of a base and in an inert organic solvent to give the compound of the formula IV 
and subsequently isomerizing the latter, for example in the presence of a base and a catalytic amount of dimethylaminopyridine (DMAP) or a cyanide source; or
b) reacting a compound of the formula XVI 
in which R2, R3, R4 and R5 have the meaning given under formula I with compounds of the formula II 
in which R6, R7, R8, R9 and W have the meaning given under formula I in an inert organic solvent in the presence of a base and a coupling agent to give the compound of the formula IV 
and subsequently isomerizing the latter, for example as described under route a).
The preparation of the compounds of the formula I is illustrated in greater detail in reaction scheme 1 below. 
The compounds of the formula I with the group Q1 in which R10 is hydroxyl can preferably be prepared in accordance with this reaction scheme. The starting material for the preparation of the compounds of the formula I in which Q is the group Q1 and R10 is hydroxyl is, in accordance with reaction scheme 1, route a), thecarboxylic acid derivatives of the formula III in which X is a leaving group for example halogen, for example iodine, bromine and, in particular chlorine, N-oxyphthalimide or N,O-dimethylhydroxylamino or part of an activated ester, for example 
(formed from dicyclohexylcarbodiimide (DCC) and the corresponding carboxylic acid) or 
(formed from N-ethyl-Nxe2x80x2-(3-dimethylaminopropyl)carbodiimide (EDC) and the corresponding carboxylic acid). These are reacted with the dione derivatives of the formula 11 in an inert organic solvent, for example a halogenated hydrocarbon, for example dichloromethane, a nitrile, for example acetonitrile, or an aromatic hydrocarbon, for example toluene, and in the presence of a base, for example an alkylamine, preferably triethylamine, an aromatic amine, for example pyridine or 4-dimethylaminopyridine (DMAP) to give the isomeric enol ethers of the formula IV. This esterification is successfully carried out at temperatures from 0xc2x0 C. to 110xc2x0 C.
The isomerization of the ester derivatives of the formula IV to give the dione derivatives of the formula I (in which R10 is OH) can be carried out, for example, in analogy to EP-A-0 353 187 or EP-A-0 316 491 in the presence of a base, for example an alkylamine, for example triethylamine, a carbonate, for example potassium carbonate, and a catalytic amount of DMAP or a catalytic amount of a cyanide source, for example acetone cyanohydrin or potassium cyanide. Both reaction steps can be carried out in situ without isolation of the intermediates IV, in particular when using a cyanide compound of the formula III (X=cyano), or in the presence of a catalytic amount of acetone cyanohydrin or potassium cyanide.
In accordance with reaction scheme 1, route b), the desired diones of the formula I (in which R10 is hydroxyl) can be obtained, for example, analogously to Chem. Lett. 1975, 1045 by esterifying the carboxylic acids of the formula XVI with the dione derivatives of the formula 11 in an inert solvent, for example a halogenated hydrocarbon, e.g. dichloromethane, a nitrile, e.g. acetonitrile or an aromatic hydrocarbon, e.g. toluene, in the presence of a base, for example an alkylamine, e.g. triethylamine, and a coupling agent, for example 2-chloro-1-methylpyridinium iodide. Depending on the solvent used, this esterification is successfully carried out at temperatures from 0xc2x0 C. to 110xc2x0 C. and first yields, as described under route a), the isomeric ester of the formula IV which can be isomerized as described under route a), for example in the presence of a base and a catalytic amount of DMAP, or a cyanide source, to give the desired dione derivatives of the formula I (R10=hydroxyl).
The activated carboxylic acid derivatives of the formula III in reaction scheme I (route a) in which X is a leaving group, for example halogen, e.g. bromine, iodine or, in particular, chlorine, can be prepared by known standard methods, for example as described by C. Ferri xe2x80x9cReaktionen der organischen Synthesexe2x80x9d [xe2x80x9cReactions in organic synthesisxe2x80x9d], Georg Thieme Verlag, Stuttgart, 1978, page 460 et seq. This is shown in the reaction scheme 2 which follows. 
In accordance with reaction scheme 2, the compounds of the formula III in which X has the abovementioned meaning are prepared, for example, by using a halogenating agent, for example thionyl halides, e.g. thionyl chloride or thionyl bromide; phosphorus halides or phosphorus oxyhalides, e.g. phosphorus pentachloride or phosphorus oxychloride, or phosphorus pentabromide or phosphoryl bromide; or oxalyl halides, for example oxalyl chloride, or by employing a reagent for forming activated esters, for example N,Nxe2x80x2-dicyclohexylcarbodiimide (DCC) or N-ethyl-Nxe2x80x2-(3-dimethylaminopropyl)carbodiimide (EDC), of the formula XVII. Examples of meanings of X for the compound of the formula XVII as halogenating agent is a leaving group, for example halogen, e.g. fluorine, bromine or iodine and, in particular, chlorine, and W1 is, for example, PCl2, SOCl, SOBr or ClCOCO.
The reaction is preferably carried out in an inert-organic solvent, for example in aliphatic, halogenated aliphatic, aromatic or halogenated aromatic hydrocarbons, e.g. n-hexane, benzene, toluene, xylenes, dichloromethane, 1,2-dichloroethane or chlorobenzene, at reaction temperatures in the range of xe2x88x9220xc2x0 C. to the reflux temperature of the reaction mixture, preferably at 40-150xc2x0 C., and in the presence of a catalytic amount of N,N-dimethylformamide. Such reactions are generally known, and various variations with regard to the leaving group X are described in the literature.
Compounds of the formula I in which R10 is other than hydroxyl or halogen can be prepared by conversion methods which are generally known from the literature, for example by acylation or carbamoylation methods using appropriate acid chlorides in the presence of a suitable base, starting from compounds in which R10 is hydroxyl, or can be prepared by nucleophilic substitution reactions on chlorides of the formula I in which R10 is halogen, which can also be obtained by known methods by reaction with a chlorinating agent such as phosgene, thionyl chloride or oxalyl chloride. In this case, examples of compounds which are employed are suitably substituted amines, or, directly, hydroxylamines, or alkylsulfonamides, mercaptans, thiophenols, phenols, Ar5xe2x80x94NH2 or Ar1xe2x80x94SH, in the presence of a base, for example 5-ethyl-2-methylpyridine, diisopropylethylamine, triethylamine, sodium bicarbonate, sodium acetate or potassium carbonate.
Compounds of the formula I in which R10 contains thio groups can be oxidized in analogy to known standard methods, for example using peracids, e.g. meta-chloroperbenzoic acid (m-CPBA) or peracetic acid, to give the corresponding sulfones and sulfoxides of the formula I. The degree of oxidation on the sulfur atom (SOxe2x80x94 or SO2xe2x80x94) can be controlled by the amount of oxidant.
Also, the resulting derivatives of the formula I in which R10 is other than hydroxyl can exist in various isomeric forms which, if appropriate, can be isolated in pure form. The invention therefore also extends to all of these stereoisomeric forms. Examples of these isomeric forms are the formulae I*, I** and I*** below in which Q is the group Q1 (see also note and scheme on page 10 above). 
All other compounds from within the scope of the formula I can be readily prepared taking into consideration the chemical properties of the pyridyl or Q moiety.
The end products of the formula I can be isolated in the customary manner by concentration or by evaporating the solvent and purified by recrystallization or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons, by distillation or by means of column chromatography and a suitable eluent.
Furthermore, the skilled worker knows in which sequence certain reactions are expediently carried out to avoid any side reactions. Unless a directed synthesis for isolating pure isomers is carried out, the product may be obtained as a mixture of two or more isomers. The isomers can be resolved by methods known per se.
Compounds of the formula I in which n is 1, i.e. the corresponding N-oxides of the formula I, can be synthesized by reacting a compound of the formula I in which n is 0 with a suitable oxidant, for example with the H2O2-urea adduct in the presence of an acid anhydride, e.g. trifluoroacetic anhydride.
Compounds of the formula I in which R in the ortho-position relative to the pyridine nitrogen is 1-chloro-C1-C2alkyl, 1-hydroxy-C1-C2alkyl, 1-(C1-C6alkylcarbonyloxy)-C1-C2alkyl, 1-benzoyloxy-C1-C2alkyl, 1-(C1-C4alkoxycarbonyloxy)-C1-C2alkyl, 1-(C1-C4alkylthio)-C1-C2alkyl, 1-(C1-C4alkylsulfinyl)-C1-C2alkyl, 1-(C1-C4alkylsulfonyl)-C1-C2alkyl, 1-thiocyanato-C1-C2alkyl, 1-cyano-C1-C2alkyl, can also be prepared by, for example, heating an N-oxide of the formula I under known reaction conditions, for example in the presence of tosyl chloride (see, for example, Parham, W. E.; Sloan, K. B.; Reddy, K. R.; Olson, P. E.; J Org Chem 1973, 38, 927) or in the presence of an acid anhydride (see, for example, Konno, K.; Hashimoto, K.; Shirahama, H.; Matsumoto, T.; Heterocycles 1986, 24, 2169) and, if appropriate, subsequently further reacting the product. These reaction sequences may be demonstrated with reference to the following example: 
Compounds of the formula I in which R in the ortho-position relative to the pyridine nitrogen, in particular 1-bromo-C1-C2alkyl, 1-chloro-C1-C2alkyl, 1-fluoro-C1-C2alkyl, 1,1-dibromomethyl, 1,1-dichloromethyl, formyl, 1-(C1-C4alkylthio)-C1-C2alkyl, 1-(C1-C4alkylsulfinyl)-C1-C2alkyl, 1-(C1-C4alkylsulfonyl)-C1-C2alkyl, 1-thiocyanato-C1-C2alkyl or 1-cyano-C1-C2alkyl, can also be prepared, for example, by oxidizing a compound of the formula I in which R10 is, in particular, chlorine, C1-C4alkoxycarbonyloxy or benzoylcarbonyloxy under known halogenation conditions, for example with N-bromosuccinimide or N-chlorosuccinimide in the presence of light and a free-radical initiator, for example benzoyl peroxide, to give the 1-bromo or 1-chloro, 1,1-dibromo or 1,1-dichloro compound, and subsequently refunctionalizing the latter to give the corresponding derivatives. Again, these reaction sequences may be demonstrated with reference to the example below. 
Compounds of the formula I can also be synthesized by reacting a compound of the formula I in which p is 0 and R2 is C1-C6alkyl with a suitable base, for example lithium diisopropylamide or n-butyllithium, at temperatures between xe2x88x92100 and xe2x88x9220xc2x0 C. (preferably xe2x88x9270 and xe2x88x9250xc2x0 C.) in an inert solvent (for example tetrahydrofuran) to give the corresponding dianion. The skilled worker knows how such carbanions can be converted by means of electrophilic substitution, for example with a chloroformic ester. This reaction sequence may be demonstrated with reference to the following example: 
Other compounds from within the scope of the formula I can be prepared with suitable electrophiles taking into consideration the chemical properties of the pyridyl or Q moiety.
The compounds of the formula IIIa 
in which
R501 is C1-C6haloalkyl;
R301 is hydrogen;
R401 is hydrogen or C1-C6alkyl; and
R210 is C1-C6alkyl, C1-C6haloalkyl-C1-C4alkyl, C2-C6alkenyl, C2-C6haloalkenyl, or C1-C2alkoxycarbonyl- or phenyl-substituted vinyl, C2-C6alkynyl or C2-C6haloalkynyl; or trimethylsilyl-, hydroxyl-, C1-C2alkoxy-, C1-C2alkoxycarbonyl- or phenyl-substituted ethynyl or C3-C6allenyl; or C3-C6cycloalkyl, halogen-substituted C3-C6cycloalkyl, C1-C4alkoxy-C1-C4alkyl, C1-C4alkyl-S(O)n4-C1-C4alkyl, cyano-C1-C4alkyl, C1-C4alkoxycarbonyl-C1-C4alkyl, C1-C4thiocyanato, oxiranyl, C1-C4alkylamino-C1-C4alkyl, C1-C4dialkylamino-C1-C4alkyl, hydroxy-C1-C4alkyl, C1-C12alkylthiocarbonyl-C1-C4alkyl or formyl-C1-C4alkyl, or R201 is a five- to ten-membered monocyclic or fused bicyclic ring system which can be aromatic or partially saturated and can contain 1 to 4 hetero atoms selected from the group consistingof nitrogen, oxygen and sulfur, the ring system being bonded to the pyridine ring via a C1-C4alkylene, xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94Cxe2x89xa1Cxe2x80x94, xe2x80x94CH2Oxe2x80x94, xe2x80x94CH2N(C1-C4alkyl)xe2x80x94, xe2x80x94CH2Sxe2x80x94, xe2x80x94CH2SOxe2x80x94 or xe2x80x94CH2SO2xe2x80x94 group and it not being possible for each ring system to contain more than 2 oxygen atoms and more than two sulfur atoms, and it being possible for the ring system itself to be mono-, di- or trisubstituted by C1-C6alkyl, C1-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C1-C6alkoxy, C1-C6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, mercapto, C1-C6alkylthio, C1-C6haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6-alkynylthio, C2-C5alkoxyalkylthio, C3-C5acetylalkylthio, C3-C6alkoxycarbonylalkylthio, C2-C4-cyanoalkylthio, C1-C6alkylsulfinyl, C1-C6haloalkylsulfinyl, C1-C6alkylsulfonyl, C1-C6-haloalkylsulfonyl, aminosulfonyl, C1-C2alkylaminosulfonyl, di-(C1-C2alkyl)aminosulfonyl, di-(C1-C4alkyl)amino, halogen, cyano, nitro, phenyl and benzylthio, it being possible for phenyl and benzylthio, in turn, to be substituted on the phenyl ring by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3-haloalkoxy, halogen, cyano or nitro, and where the substituents on the nitrogen in the heterocyclic ring are other than halogen; and
X is halogen or cyano, are novel and were developed specifically for the preparation of the compounds of the formula I and are therefore a further subject of the present invention.
The compounds of the formula XVIa 
in which R201, R301, R401 and R501 have the abovementioned meaning, with the proviso that, if R501 is trifluoromethyl and, simultaneously, R301 and R401 are hydrogen, then R201 is other than C1-C6alkyl, are novel and therefore a further subject of the present invention.
The compounds of the formula Q1 (or formula II) are known and can be prepared by methods similar to those described, for example in J. Org. Chem. (1977), 42, 1163-9, Brit. UK Pat. Appl. GB 2205316, DE 3902818, GB 8706557, DE 4434987, WO 9213821 and Aust. J. Chem. (1976), 29(11), 2525-31, Chem. Commun. (1998), (16), 1691-1692.
The compounds of the formula XVI (or XVIa and XVIb) are synthesized by methods similar to known methods, for example as in Heterocycles, 46, 129 (1997) or Helvetica Chimica Acta 71, 596 (1988), and is characterized in that either
a) a compound of the formula V 
in which R301 is hydrogen;
R401 is hydrogen, C1-C6alkyl or phenyl, it being possible for phenyl, in turn, to be substituted by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro;
or R401 is a five- to ten-membered monocyclic or fused bicyclic ring system which can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur and it not being possible for the ring system to contain more than 2 oxygen atoms and more than two sulfur atoms, and it being possible for the ring system itself to be mono-, di- or trisubstituted by C1-C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C1-C6alkoxy, C1-C6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, C1-C6alkylthio, C1-C6haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, C1-C4alkoxy-C1-C2alkylthio, C1-C4alkylcarbonyl-C1-C2alkylthio, C1-C4alkoxycarbonyl-C1-C2-alkylthio, cyano-C1-C4alkylthio, C1-C6alkylsulfinyl, C1-C6haloalkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylsulfonyl, aminosulfonyl, C1-C2alkylaminosulfonyl, di-(C1-C2alkyl)aminosulfonyl, halogen, cyano, nitro, phenyl and benzylthio, it being possible for phenyl and benzylthio, in turn, to be substituted on the phenyl ring by C1-C3alkyl, C0-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro, and where substituents on the nitrogen in the heterocyclic ring are other than halogen; and
R14 is C1-C4alkyl;
is acylated with a compound of the formula VI 
in which R501 is C1-C6haloalkyl to give the compound of the formula VII 
in which R301, R401, R501 and R14 have the abovementioned meaning in the presence of a base, for example an aromatic amine, e.g. pyridine, and the alkoxy group is subsequently exchanged for the amino group with ammonia in an organic solvent, for example a halogenated hydrocarbon, e.g. dichloromethane, a nitrile, e.g. acetonitrile. The resulting compound of the formula VIII 
is subsequently subjected to a condensation reaction with a compound of the formula IX 
in which R201 is C1-C6alkyl, C1-C6haloalkyl-C1-C4alkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C3-C6cycloalkyl, C1-C4alkoxy-C1-C4alkyl, C1-C4alkyl-S(O)n4xe2x80x94C1-C4alkyl, cyano-C1-C4alkyl, C1-C4alkoxycarbonyl-C1-C4alkyl, C1-C4alkoxycarbonyloxy-C1-C4alkyl, C1-C4thiocyanato-C1-C4alkyl, oxiranyl, C1-C4alkylamino-C1-C4alkyl, di-(C1-C4alkyl)amino-C1-C4alkyl or formyl-C1-C4alkyl;
or R201 is a group Ar6xe2x80x94C1-C4alkyl in which Ar6 is a five- to ten-membered monocyclic or fused bicyclic ring system which can be aromatic or partially saturated and can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it not being possible for each ring system to contain more than 2 oxygen atoms and more than two sulfur atoms and it being possible for the ring system itself to be mono-, di- or trisubstituted by C1-C6alkyl, C1-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C1-C6alkoxy, C1-C6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, mercapto, C1-C6alkylthio, C1-C6haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6-alkynylthio, C2-C5alkoxyalkylthio, C3-C5acetylalkylthio, C3-C6alkoxycarbonylalkylthio, C2-C4-cyanoalkylthio, C1-C6alkylsulfinyl, C1-C6haloalkylsulfinyl, C1-C6alkylsulfonyl, C1-C6-haloalkylsulfonyl, aminosulfonyl, C1-C2alkylaminosulfonyl, di-(C1-C2alkyl)aminosulfonyl, di-(C1-C4alkyl)amino, halogen, cyano, nitro, phenyl and benzylthio, it being possible for phenyl and benzylthio, in turn, to be substituted on the phenyl ring by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro, and where substituents on the nitrogen in the heterocyclic ring are other than halogen, and R14 has the abovementioned meaning, and subsequently hydrolysing the resulting compound of the formula Xa 
is subsequently hydrolysed to give the compound of the formula XVIa 
in which R201, R301, R401 and R501 have the abovementioned meaning; or
b) a compound of the formula XI 
in which R14 has the abovementioned meaning is subjected to a condensation reaction with a compound of the formula XII. 
and the resulting compound of the formula XIII 
in which R3, R4 and R5 have the abovementioned meaning and R14 is C1-C4alkyl, is chlorinated to give the compound of the formula XIV 
in which R3, R4, R5 and R14 have the abovementioned meaning (for example using POCl3), and this compound is subsequently reacted with a nucleophile of the formula XV
Zxe2x80x94R15xe2x80x83xe2x80x83(XV)
in which Z is SH, OH or amino and R15 is C1-C6alkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C1-C6alkylsulfonyl, C1-C6haloalkyl, phenyl or benzyl, it being possible for the phenyl group, in turn, to be substituted by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro, or is C1-C4alkoxy-C1-C4alkyl, C1-C4alkylthio-C1-C4alkyl, C1-C4alkylsulfinyl-C1-C4alkyl, C1-C4alkylsulfonyl-C1-C4alkyl, C1-C4alkylsulfonyl or di-(C1-C4alkyl)aminosulfonyl, or R15 is a five- to ten-membered monocyclic or fused bicyclic ring system which can be aromatic or partially saturated and can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it not being possible for each ring system to contain more than 2 oxygen atoms and more than two sulfur atoms and it being possible for the ring system itself to be mono-, di- or trisubstituted by C1-C6alkyl, C1-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C1-C6alkoxy, C1-C6-haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, mercapto, C1-C6alkylthio, C1-C6-haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, C2-C5alkoxyalkylthio, C3-C5acetylalkylthio, C3-C6alkoxycarbonylalkylthio, C2-C4cyanoalkylthio, C1-C6alkylsulfinyl, C1-C6haloalkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylsulfonyl, aminosulfonyl, C1-C2alkylaminosulfonyl, di-(C1-C2alkyl)aminosulfonyl, (CH2)nR7, NR8R9, halogen, cyano, nitro, phenyl and benzylthio, it being possible for phenyl and benzylthio, in turn, to be substituted on the phenyl ring by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro, and substituents on the nitrogen in the heterocyclic ring being other than halogen, in the presence of a base to give compounds of the formula Xb 
in which R14, R15, R3, R4, R5 and Z have the abovementioned meanings and the resulting compound is subsequently hydrolysed to give the compound of the formula XVIb 
in which R15, R3, R4, R5 and Z have the abovementioned meaning.
Compounds in which Zxe2x80x94R15 and Z are oxygen and R15 is C1-C6alkyl, C3-C6alkenyl, C3-C6alkynyl, C1-C6haloalkyl, C3-C6haloalkenyl, cyano-C1-C4alkyl, C1-C4alkoxy-C1-C4alkyl, C1-C4alkylthio-C1-C4alkyl or C1-C4alkoxycarbonyl-C1-C4alkyl can also be reacted starting from XIII by direct alkylation with the corresponding alkylating agent Lxe2x80x94R15 XVa in which L is a leaving group such as chlorine, bromine, iodine, mesyloxy or tosyloxy.
Compounds of the formula XVIb in which Zxe2x80x94R15 is fluorine are prepared by reacting a compound of the formula XIV with potassium fluoride and, if appropriate, a catalytic amount of 18-crown-6 in the presence of a polar aprotic solvent, for example acetonitrile, dimethylformamide or sulfolane. Compounds of the formula XVIc in which Zxe2x80x94R15 is hydrogen are prepared by reducing the chlorine group in formula XIV, for example with hydrogen in the presence of a suitable metal catalyst or with ammonium formate, in a suitable solvent. The preparation of the compounds of the formula XVI or XVIa, XVIb and XVIc are illustrated in greater detail in reaction schemes 3 and 4 which follow. 
Compounds of the formula XVId in which R2 is bromomethyl, cyanomethyl, thiocyanatomethyl, C2-C6alkenyl, C2-C6haloalkenyl, a C1-C2alkoxycarbonyl- or phenyl-substituted vinyl, C2-C6alkynyl, C2-C6haloalkynyl, a trimethylsilyl-, hydroxyl-, C1-C2alkoxy-, C1-C2alkoxycarbonyl- or phenyl-substituted ethynyl, C3-C6allenyl, C3-C6cycloalkyl or mono- or polyhalogenated C3-C6cycloalkyl can be prepared, for example, in accordance with generally known conversion methods which are shown in reaction scheme 4a. 
Intermediates of the formula XVIa in which R501 is CF2Cl are prepared as described in scheme 3 or by reacting a compound of the formula Xa in which R501 is trichloromethyl with hydrofluoric acid in a pressurized vessel at temperatures between 0 and 220xc2x0 C. (preferably 60-200xc2x0 C.).
Compounds of the formula XVIa in which R501 is CHF2 can be prepared as in scheme 3 or by heating a compound of the formula Xa in which R301, R401, R14 and R201 have the abovementioned meaning and R501 is CF2Cl in an inert solvent, for example toluene or benzene, at temperatures between 25 and 120xc2x0 C. (preferably 80-120xc2x0 C.) with tributyltin hydride or 1,1,1,3,3,3-hexamethyl-2-(trimethylsilyl)trisilane in the presence of a catalytic amount of azo-isobutyronitrile and subsequently hydrolysing the resulting compound to give the compound of the formula XVIa in which R501 is CHF2.
Compounds of the formula XVIa in which R201, R301, R401 and R501 have the abovementioned meaning can also be prepared by reacting a compound of the formula Xc in which R14, R301, R401 and R501 have the abovementioned meaning and R201 is CH2Cl by nucleophilic substitution, for example with an alkali metal iodide in an inert solvent, to give the corresponding iodides, or by means of gaseous hydrobromic acid in lower carboxylic acids such as glacial acetic acid to give the corresponding bromine derivatives (for example in accordance with U.S. Pat. No. 3,974,166) or by means of alkali metal fluoride in a dipolar solvent such as sulfolane to give the corresponding fluorine derivatives, or, to prepare an alkoxy radical Xd, by reacting a halogen derivative Xc with an alcohol or phenol in the presence of a base such as sodium hydride or an alkaline earth metal oxide or alkaline earth metal carbonate or directly with an alkali metal alkoxide in an inert solvent such as dimethylformamide or in an excess of the alcohol ROH which corresponds to the group to be introduced at temperatures between xe2x88x925 and 160xc2x0 C.,
or, in order to prepare a corresponding aromatic or aliphatic thioether Xe, by reacting, analogously to what has been said above, either the halide Xc with an aliphatic or aromatic thiol in the presence of a base such as sodium hydride or with an alkali metal salt of a thiol in an inert solvent at xe2x88x9210-150xc2x0 C., or, in order to prepare corresponding sulfinyl or sulfonyl derivatives Xe, by carrying out the reaction with an oxidant such as m-chloroperbenzoic acid or sodium periodate or sodium perborate, with the temperature control known in the art, depending on the degree of oxidation (for example xe2x88x9230xc2x0 C.-+50xc2x0 C. for n=1) or xe2x88x9220xc2x0 C.-+100xc2x0 C. for n=2) in an inert solvent such as dichloromethane to give Xf,
or, in order to prepare cyanomethylene derivatives of the formula Xg, by reacting a halide of the formula Xc with an alkali metal cyanide or tetraalkylammonium cyanide or copper cyanide in an inert solvent such as dichloromethane, tetrahydrofuran or dimethylformamide at temperatures between 0xc2x0 C. and 220xc2x0 C.
The preparation of the compounds of the formula XVIa (R501=CF2Cl) and of the intermediates of the formulae Xc, Xd, Xe, Xf, and Xg are illustrated in greater detail in the reaction schemes 5, 6 and 7 which follow. 
To prepare all other compounds of the formula X and XVI which are functionalized in accordance with the definition of R201 (Zxe2x80x94R15) to R501, a multiplicity of known standard methods are suitable, for example alkylation, halogenation, acylation, amidation, oximation, oxidation and reduction, the choice of the preparation methods which are suitable depending on the properties (reactivities) of the substituents in the intermediates.
The reactions to give compounds of the formula I are advantageously carried out in aprotic inert organic solvents. Such solvents are hydrocarbons such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons such as dichloromethane, trichloromethane, tetrachloromethane or chlorobenzene, ethers such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitrites such as acetonitrile or propionitrile, amides such as N,N-dimethylformamide, diethylformamide or N-methylpyrrolidinone. The reaction temperatures are advantageously between xe2x88x9220xc2x0 C. and +120xc2x0 C. In general, the reactions are slightly exothermic and, as a rule, they can be carried out at room temperature. To shorten the reaction time, or else to start the reaction, the mixture may be heated briefly to the boiling point of the reaction mixture. The reaction times can also be shortened by adding a few drops of base as reaction catalyst. Suitable bases are, in particular, tertiary amines such as trimethylamine, triethylamine, quinuclidine, 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene or 1,5-diazabicyclo-[5.4.0]undec-7-ene. However, inorganic bases such as hydrides, e.g. sodium hydride or calcium hydride, hydroxides, e.g. sodium hydroxide or potassium hydroxide, carbonates such as sodium carbonate and potassium carbonate, or hydrogen carbonates such as potassium hydrogen carbonate and sodium hydrogen carbonate, may also be used as bases. The compounds of the formula I can be isolated in the customary manner by concentrating and/or by evaporating the solvent and purified by recrystallization or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons.
All application methods which are conventionally used in agriculture, for example pre-emergence application, post-emergence application and seed treatment, as well as various methods and techniques, for example the controlled release of active ingredients, are suitable for the use according to the invention of the compounds of the formula I or of compositions comprising them. To this end, the active ingredient in solution is applied to mineral carriers for granules or to polymerized granules (urea/formaldehyde) and dried. If appropriate, an additional coating can be applied (coated granules), which allows the active ingredient to be released in a controlled manner over a specific period of time.
The compounds of the formula I can be employed as herbicides as such, i.e. as obtained from synthesis. However, they are preferably processed in the customary manner together with the auxiliaries conventionally used in the art of formulation, for example to give emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. Such formulations are described, for example, in WO 97/34485 on pages 9 to 13. The application methods such as spraying, atomizing, dusting, wetting, scattering or pouring, as well as the type of composition, are chosen to suit the intended aims and the prevailing circumstances.
The formulations, i.e. the compositions, preparations or products which comprise the active ingredient of the formula I or at least one active ingredient of the formula I and, as a rule, one or more solid or liquid formulation auxiliaries are prepared in the known manner, for example by intimately mixing and/or grinding the active ingredients together with the formulation auxiliaries, for example solvents or solid carriers. Furthermore, surface-active compounds (surfactants) may additionally be used when preparing the formulations. Examples of solvents and solid carriers are indicated for example in WO 97/34485 on page 6.
Suitable surface-active compounds are, depending on the nature of the active ingredient of the formula I to be formulated, non-ionic, cationic and/or anionic surfactants and surfactant mixtures which have good emulsifying, dispersing and wetting properties.
Examples of suitable anionic, non-ionic and cationic surfactants are enumerated, for example, in WO 97/34485 on pages 7 and 8.
The surfactants conventionally used in the art of formulation which are described, inter alia, in xe2x80x9cMcCutcheon""s Detergents and Emulsifiers Annualxe2x80x9d MC Publishing Corp., Ridgewood N.J., 1981, Stache, H., xe2x80x9cTensid-Taschenbuchxe2x80x9d [xe2x80x9cSurfactants Guidexe2x80x9d], Carl Hanser Verlag, Munich/Vienna, 1981, and M. and J. Ash, xe2x80x9cEncyclopedia of Surfactantsxe2x80x9d, Vol I-III, Chemical Publishing Co., New York, 1980-81, are furthermore also suitable for preparing the herbicidal compositions according to the invention.
As a rule, the herbicidal formulations comprise 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of herbicide, 1 to 99.9% by weight, in particular 5 to 99.8% by weight, of a solid or liquid formulation auxiliary and 0 to 25% by weight, in particular 0.1 to 25% by weight, of a surfactant. While concentrated compositions are more preferred as commercially available goods, the end consumer uses, as a rule, dilute compositions. The compositions can also comprise further additives such as stabilizers, for example epoxidized or non-epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soya oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders, tackifiers and fertilizers or other active ingredients.
As a rule, the active ingredients of the formula I are applied to the plant or its environment at rates of 0.001 to 4 kg/ha, in particular 0.005 to 2 kg/ha. The dosage required for the desired action can be determined by experiments. It depends on the type of the action, the developmental stage of the crop plant and of the weed, and on the application (location, timing, method) and can, owing to these parameters, vary within wide limits.
The compounds of the formula I are distinguished by herbicidal and growth-inhibitory properties which allow them to be employed in crops of useful plants, in particular in cereals, cotton, soya, sugar beet, sugar cane, plantation crops, rapeseed, maize and rice and for the non-selective control of weeds. Crops are also to be understood as including those which have been rendered tolerant to herbicides or classes of herbicides by means of conventional plant breeding or by genetic engineering methods. The weeds to be controlled may be both mono- and dicotyledonous weeds such as Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa,_Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.